JP3241136B2 - Composition containing low caries-inducing hydrogenated saccharide, method for producing the same and application field - Google Patents

Abstract

Low-cariogenic hydrogenated saccharide composition usable as sweetening composition or as a texture agent in food products and in certain pharmaceutical or veterinary products. This composition is characterised in that it has a hydrogenated monosaccharide content of 0.1 to 80 %, a hydrogenated disaccharide content of 0.1 to 96 %, a hydrogenated mono- and disaccharide content of 11 to 96 %, a content of 1 to 40 % of polysaccharides which cannot be hydrolysed by amyloglucosidase, the remainder to 100 % consisting of hydrogenated oligosaccharides or polysaccharides.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a low cariogenic hydrogen used as a sweetening composition or as a drug in products consumed by humans and animals, i.e. foods, pharmaceutical or veterinary products. The present invention relates to a composition comprising a saccharide.

[0002] The invention also relates to a process for producing the composition and to the field of application of the composition in products for human or animal consumption.

[0003]

BACKGROUND OF THE INVENTION The expression "products taken by humans and animals" refers to products intended for ingestion or oral administration, such as confectionery products, pastries, creams, beverages, jams, sauces, ice creams, animal feeds and the like. Various groceries,
It also refers to pharmaceutical, veterinary, dietary or health products such as elixirs, cough syrups, candy and tablets, chewing pastes, chewing gums, pastilles, mouthwashes, toothpastes and gels. Is understood.

[0004] The expression "low caries-inducing hydrogenated saccharides" means hydrogenated saccharides which cause less acidification by bacteria present in the mouth than conventional sugars such as sucrose, glucose and fructose. Is understood to be.

[0005] Such low caries-inducing hydrogenated saccharides are already known. For example, sorbitol, xylitol, maltitol, erythritol, lactitol, hydrogenated isomaltulose (trade name PALATINIT, or more commonly known as ISOMALT), mannitol, arabitol, threitol, isomaltitol and the like. is there.

[0006] Syrups containing some of these various products are already commercially available. For example, sorbitol syrup, LYCASI marketed by the applicant's company
Maltitol syrup containing 50-55% maltitol, such as N 80/55, about 72% dry matter, such as MALTISORB 75/75 marketed by the applicant's company.
There are maltitol syrups sold under trade names such as maltitol syrup containing up to 78% maltitol, MALTIDEX 100, MALTIDEX 200, MALBIT, FINMALT.

[0007]

However, none of the aforementioned products, or mixtures of these various products, fulfills all the desirable qualities, advantages and technical properties of a low caries-inducing sweetening composition. .

Indeed, some of the aforementioned products, such as sorbitol, maltitol, xylitol, erythritol, mannitol, have a disadvantageous tendency to crystallize when used in high strength and high concentrations. This crystallization makes them unsuitable for use in many food and pharmaceutical and veterinary products.

In addition, some products, such as mannitol, lactitol, threitol, hydrogenated isomaltulose, do not have a very high sweetening capacity. Although they have found evident sweetness earlier than others, they limit their application in confectionery products and pharmaceutical syrups. For this reason, it is necessary to add artificial sweeteners such as saccharin, aspartame, cyclamate, and acesulfame K. However, these artificial sweeteners are relatively expensive products and are unstable.

[0010] However, there are some products that have high sweetening ability and are difficult to crystallize. This is the case, for example, with some maltitol syrups. Nevertheless, these syrups have the major problem of not providing sufficient viscosity to the products used. Viscosity is required in products such as chew pastes, candy, nougat, pharmaceutical syrups, elixirs, toothpastes.

In addition, some of the hydrogenated products mentioned above are very hygroscopic. This is particularly problematic in the production of candy. Manufactured candy tends to contain water and has the problem of sticking to wrapping paper.

[0012] Moreover, while it is desirable to have the obvious advantage of being able to alter the activity of water in a sweetening composition as a function of secondary use, at present,
Even using a mixture of two or three hydrogenation products of the foregoing, this is not possible.

Finally, for some applications, the boiling point of the sweetening composition can be freely changed, the hygroscopicity adjusted, or the glass transition temperature or freezing point optionally adjusted in a given direction. It is desirable to be able to do it.

[0014] Therefore, in the food industry, pharmaceutical or veterinary industry, the following very obvious requirements are made for sweetening compositions. Low cariogenicity (low caries generation) and high enzyme stability. Have high sweetness ability. Not necessarily requiring artificial sweeteners, which can cause unpleasant sensations and limit thermal stability. Excellent technical properties in all application fields. Be compatible with, or, where appropriate, any of, these ingredients used in the ingested product or mixed before use. Easy control of water activity depending on the application faced. The ability to change hygroscopicity, glass transition temperature, freezing point and boiling point depending on the chosen application field. To give the final product acceptable "mechanical" properties and texture,
Have sufficient viscosity and texture. No additional or auxiliary products need to be added. No danger of crystallization in the application field. Such a risk is disadvantageous. Conversely, in some applications, limited controlled crystallization can be induced. Fine crystallization or graining on the surface is intentionally found.

However, by developing and developing new compositions containing low caries-inducing hydrogenated saccharides, Applicant's company has great value in satisfying all of the many qualities and properties that have heretofore been incompatible. I got it.

[0016]

According to the present invention, a composition containing a low cariogenic hydrogenated saccharide according to the present invention is characterized by the following expression in terms of concentration by weight based on the dry matter of the composition. The concentration of hydrogenated monosaccharide is 0.1 to 80
%, Preferably 0.1 to 75%, more preferably 0.1.
７０70%, the concentration of hydrogenated disaccharide is 0.1-96 by weight
%, Preferably 0.2 to 94%, more preferably 0.3%.
~ 90%, the concentration of hydrogenated monosaccharides and hydrogenated disaccharides is
11-96% by weight, preferably 22-94%, more preferably 35-90%, F-test (described below)
The concentration of polysaccharide not hydrolyzed by amyloglucosidase is 1 to 40% by weight, preferably 1.5 to 3%.
0%, more preferably 3-26.5%, and 100% balance with hydrogenated oligosaccharides and polysaccharides.

The hydrogenated monosaccharide is selected from the group comprising sorbitol, mannitol, galactitol, xylitol, threitol, arabitol and erythritol.

Hydrogenated disaccharides include maltitol, hydrogenated maltulose, hydrogenated isomaltulose (glucopyranoside-1,6-mannitol and glucopyranoside-1,6-
Sorbitol), isomaltitol, lactitol, and hydrogenated inurobiose.

The hydrogenated oligosaccharides and polysaccharides comprise maltotriitol, maltotetriitol and other hydrogenated oligosaccharides and polysaccharides obtained by hydrogenation followed by hydrolysis of starch. However, the above-mentioned hydrogenated oligosaccharides and polysaccharides are composed of cellobiitol, cellotriitol, xylobiitol, xylotriitol, inulotriitol, and hydrogenated oligosaccharides and polysaccharides obtained by hydrolysis. This hydrolysis is generally the acid hydrolysis of a fractance such as inulin obtained by cellulose, xylans, and hydrogenation.

To determine the concentration of polysaccharide in the composition that is not hydrolyzed by the enzyme amyloglucosidase,
An F test is performed. What is F-test?
O. Box 14508, St. Louis, MO 63178 USA Developed by the United States and is equivalent to a test for the determination of “comprehensive food fiber”, the Sigma Technical Note No. TDFAB-
This is described in detail in 1.

This test essentially determines the amount of components in the hydrolyzate that are not hydrolyzed by amyloglucosidase in the presence of thermostable α-amylase and protease. This amount is expressed as a percentage of about 1 g of the hydrolyzate completely dried under vacuum at 70 ° C. overnight.

The procedure for executing this test is as follows. 1) Four samples of about 1 g of the hydrolyzate completely dried under vacuum and cooled in a desiccator all day and night are weighed in 0.1 mg portions and placed in a 400 ml deep beaker. 2) 50m phosphate buffer (0.05M) at pH 6.0
1 to each of the four beakers. 3) Add 0.05 ml of a solution of α-amylase (No. A 3306 manufactured by Sigma) to each beaker and mix thoroughly. 4) Cover each beaker with aluminum foil, immerse it in a boiling water bath, measure after beaker temperature reaches 95 ° C., and incubate for 30 minutes. The mixture is gently stirred at regular intervals of 5 minutes. 5) Cool the solution to room temperature. 6) Adjust the pH of the solution to 7.5 ± 0.1 by adding 0.171N, 10 ml of NaOH to each beaker. Check the pH and add sodium hydroxide (0.
171N) or phosphoric acid (0.205M). 7) 5 mg of protease powder (No.P-391 manufactured by Sigma)
Add 0) to each beaker. 8) Cover the beaker with aluminum foil and incubate the solution at 60 ° C. for 30 minutes with continuous stirring. 9) Cool the mixture to room temperature. 10) Add 10 ml of 0.205 M H ₃ PO ₄ to each beaker and adjust the pH of the solution to 4.5 ± 0.2. pH
And adjust with a sodium hydroxide or phosphoric acid solution as appropriate. 11) 0.3 ml of amyloglucosidase (manufactured by Sigma)
No.A.9913) to each beaker. 12) Cover each beaker with aluminum foil and incubate at 60 ° C. for 30 minutes while stirring. The culture time was measured from the time the internal temperature of the beaker reached 60 ° C.
0 minutes. 13) Add 280 ml of 95% (volume ratio) ethanol preheated to 60 ° C. to each beaker. (95% (volume ratio) ethanol contains 50 ml of demineralized water at 1000C at 20 ° C and the remainder pure alcohol.) 14) Precipitate the mixture at room temperature for at least 60 minutes or all day and night. Formed on standing (all four samples are left for the same time). 15) Vacuum filter the contents of each beaker over a celite bed of a sintered glass crucible and carefully wash in the following order. Perform three times with 20 ml of 78% (volume ratio) ethanol. (78% (volume ratio) ethanol is 100
At 0 ml, 220 ml of demineralized water was contained, and the remainder was pure alcohol. ) 95% (volume ratio) ethanol 10m
Wash twice with l. Wash twice with 10 ml of acetone. 16) Dry the four filters overnight at 70 ° C. under vacuum conditions. 17) Cool the filters in a desiccator and weigh the filters to within 0.1 mg. This weight corresponds to the sum of the weight of the filtration residue (polysaccharide, protein, ash not hydrolyzed by amyloglucosidase) and the weight of the crucible with celite. 18) Two samples of the filtration residue obtained from the four samples are determined according to the Kjeldahl method with a correction coefficient of 6.25 to determine the protein enrichment. 19) For the remaining two filtration residues, place these crucibles in a 525 ° C. oven for 5 hours and measure the ash content. 20) The amount of polysaccharide not hydrolyzed by amyloglucosidase is calculated on four samples as indicated in the Sigma Technical Note above. The average calculated from these quantities is expressed as corresponding to the average weight of the hydrolyzate feed dried at 70 ° C. in a vacuum overnight. At this time, a blank test (containing no dried hydrolyzate) of four samples is performed in parallel, and the results are incorporated into the calculation.

This F test is described in "J. Assoc. Off. Anal.
Chem., Vol 68, No. 2, 1985, p399 is a variation of the test method for determining total dietary fiber in foods.

In order to standardize this test, perform iteratively and repeatedly and make the results reproducible, it is desirable to use an entire analysis kit.

The components according to the process of the invention can also be represented by another test method called the A test, which measures the concentration of polysaccharides which are precipitated in ethanol and not hydrolyzed by amyloglucosidase. The method of the A test is shown below.

A 10 g sample of the sweetener obtained according to the present invention is adjusted to 75 ± 0.2 Brix by hydrogenation or evaporation and dehydration so that the refractive index becomes 1.478. This sample is used for digestion of hydrogenated polysaccharides precipitated by ethanol. Brix is a unit of measurement commonly used in the starch food industry, and syrup Brix is easily determined by refractometer. For the composition of the present invention, 75 Brix is about 75
% Dry matter.

A 10 g sample of the 75 brix sweet composition obtained in the present invention was added to 30 cm ³ of distilled water and 60 c
Add anhydrous alcohol m ^3. The mixture is left at 0 ° C. for 1 hour. And 10000 for 15 minutes at 0 ° C.
Centrifuge at g. The obtained pellets are dried at 80 ° C. in a vacuum dryer. Weight of the precipitate obtained, P1
Indicates the weight of polysaccharide that can be precipitated in ethanol contained in the initial sample of 10 g, and is about 7.5 g dry matter.

In the sweetening compositions of the present invention, the A test is used to determine the concentration of hydrogenated polysaccharides that precipitate with ethanol and are not hydrolyzed by amyloglucosidase. In the A test, the polysaccharide precipitated in ethanol obtained above is subjected to an enzyme treatment using a heat-resistant α-amylase, protease, and amyloglucosidase. The unhydrolyzed polysaccharide is precipitated with 95% ethanol, the resulting precipitate is filtered, the filtrate is washed with alcohol and acetone, and the final residue weight, P2, is determined.

This test was performed in accordance with “J. ASSOC. OF ANAL. CHEM.” Vol. 68, No. 2, 19
85, p. 339.

The composition containing a hydrogenated saccharide having a low caries-inducing property according to the present invention has the following characteristics.
Concentrations are expressed by weight of the composition on dry matter.
The concentration of hydrogenated monosaccharide is 0.1-65%, preferably 0.1%.
It is 1 to 60%, more preferably 0.1 to 55%.
The concentration of hydrogenated disaccharide is 10-96% by weight, preferably 15-94%, more preferably 15-90%. The concentration of polysaccharide precipitated by ethanol and not hydrolyzed by amyloglucosidase in the aforementioned A test is 1 to 30% by weight, preferably 1.5 to 25%,
More preferably, it is 2 to 15%.

By simultaneously selecting the concentrations of hydrogenated monosaccharides, disaccharides, oligosaccharides and polysaccharides, it is possible to obtain a sweetening composition with all the qualities required in many fields of application: Essentially due to the presence of hydrogenated polysaccharide concentrations that are not hydrolyzed by amyloglucosidase. here,
The quality required in many applications is, for example,
No crystallization, possibility of adjusting viscosity, boiling point, glass transition temperature, freezing point, hygroscopicity and sweetness ability.

In order to produce a sweet composition according to the present invention, the following method or a method similar thereto is carried out.

First, a fraction containing a polysaccharide that is not digested by amyloglucosidase is prepared. To do this, at least one of dextrin or polyglucose is subjected to an enzymatic treatment, including at least a saccharifying enzyme action, for example amyloglucosidase or β-amylase. The conditions for this treatment are as follows: dextrin or polyglucose hydrolyzate obtained at the end of this treatment
E is 5 to 80, preferably 10 to 65,
It is also determined that the hydrolyzate obtained is hydrogenated and further purified itself by known methods.

The phrase "polyglucosidase" is understood to mean a product having 1-6 linkages obtained by condensation or rearrangement from glucose or one or more sugars. It is also reduced in combination with the action of heat and acid under substantially water-free conditions. Such polymers have been described many times until now, in particular in patents US Pat. No. 2,436,967, US Pat.
766, 165, US 4, 965, 354, US 5, 051, 500, JP 01-
12761, JP 02-163101. Preferably, these polymers can be obtained from glucose and citric acid, optionally in the presence of sorbitol.

[0035] Within the scope of the present invention, the phrase "dextrin" means a product obtained by heating starch while adjusting the humidity to a low level, generally in the presence of an acidic or basic catalyst. Is understood. This "dry roasting" of starch is most commonly carried out in the presence of an acid, but both depolymerization of the starch and condensation of the residual starch obtained occur, resulting in
Highly branched molecules are produced. Dextrins are one of the oldest starch derivatives, and their manufacture and field of application, along with their properties, are described for various dextrins, for example, in “Starch Chemistry and Technolog
y ”-Second Edition-Edited by RoyL. WHISTLER
-1984-Academic Press Inc.

The enzymatic treatment of dextrin has already been proposed, for example, in European Patent No. 0368451 or JP-A-62091501, but has been used for other purposes. These technical documents will be interpreted in more detail later.

Dextrin obtained by dry roasting starch in the presence of an acid catalyst such as hydrochloric acid is
It is desirable to use also in the production of the composition of the present invention. The acid is thus sprinkled on the starch and the resulting mixture is stirred until the water content is less than or equal to about 5%.
For example, preliminary drying is performed at a temperature of 80 to 130 ° C. afterwards,
At the end of the reaction, the mixture is "roasted" at a temperature of about 140-250C for about 30 minutes to about 6 hours to obtain a dextrin having a DE of about 0.5 to 10. Any type of starch, especially corn starch, potato starch,
Wheat starch, cassava starch, rice starch or pea starch can also be used in the production of these dextrins.

According to ISO 1227 of 1979, dextrin can be obtained from starch or starch wheat modified by heating in the dry state, with or without the addition of small amounts of chemical reagents. Traditionally, dextrins fall into two categories: white dextrins, which are not particularly difficult to produce from raw materials, and those produced under more stringent conditions, whose color depth is a degree of improvement from the natural structure Is a yellow dextrin. Dextrins are essentially α-
Hydrolysis of the 1-4 bonds occurs, and at elevated temperatures, condensation, hydrolysis of glycosidic bonds, and anhydration reactions occur.

The applicant's company has TACKIDEX DF 165, TAC
Dextrins such as those marketed under the trade names KIDEX DF 155 and TACKIDEX JO 55K can be suitably used.

Then, a selected one of dextrin, polyglucose or a mixture of dextrin and polyglucose is suspended in water at a dry matter content of 20 to 70%, preferably 20 to 45%, to give amyloglucosidase. And / or saccharification using at least one saccharifying enzyme consisting of β-amylase.

Although this is not necessary in all cases, it is desirable that the enzymatic action of β-amylase and / or amyloglucosidase be performed before the action of α-amylase, which is thermostable.

Similarly, the saccharification treatment may be performed after the action of α-amylase or simultaneously with the action.

According to a preferred method, the treatment can be carried out using an enzyme that hydrolyzes the 1-6 bond of amylopectin, for example, isoamylase or pullulanase. This treatment using an enzyme that hydrolyzes the 1-6 bond of amylopectin may be performed before, simultaneously with, or after the saccharification treatment, and the enzyme is performed only on polysaccharides that are difficult to digest enzymatically, It is particularly effective in the area of action which makes it possible to leave the dextrin and / or the hydrolyzate of the polyglucose obtained.

The enzymatic action of amyloglucosidase, β-amylase and any α-amylase, pullulanase or isoamylase on dextrin, polyglucose or a mixture thereof is determined by glucose, maltose, maltotriose and other oligosaccharides. And a polysaccharide, in addition to a fraction containing a polysaccharide that is not digested by amyloglucosidase.

This fraction is used to increase the concentration of polysaccharides that are not digested by amyloglucosidase,
Immediately hydrogenation or additional treatment is applied. Examples of such treatment include membrane separation techniques such as reverse osmosis and ultrafiltration, precipitation techniques using a solvent, and chromatographic separation. Substantial separation of the polysaccharides can also be facilitated by chromatographic separation on a cationic resin or zeolite converted to an alkali metal or alkaline earth metal form.

It goes without saying that such a chromatographic separation can be carried out before the hydrogenation and subsequently the polysaccharides which are not digested by amyloglucosidase need to be hydrogenated. However, according to a preferred embodiment of the present invention, the chromatographic enhancement or separation of the polysaccharide is performed after the hydrogenation. This makes it possible to produce a composition comprising hydrogenated saccharides according to the invention, merely by performing a hydrotreatment. Still further, the separation of the polysaccharide is more effective in this case.

Thus, a fraction containing a polysaccharide not hydrolyzed by amyloglucosidase is obtained,
The sweetening composition according to the invention can then be produced.

Thus, starting from a fixed proportion of the composition, this proportion obviously depends on the concentration of the polysaccharide in said fraction and any hydrogenated monosaccharide, disaccharide , Oligosaccharides and polysaccharides are added in fixed proportions to each of the constituent groups.

According to the first variant, these are added to the fraction of non-hydrogenated polysaccharides obtained at the end of the enzymatic treatment of dextrin and polyglucose or a mixture thereof, and then added to the non-hydrogenated monosaccharides. , Disaccharides or oligosaccharides and polysaccharides are subjected to chromatographic high concentration or fractional treatment in accordance with the ratio determined for each of these components. Then, the composition thus obtained is hydrogenated.

According to the second variant, preferably, the polysaccharide fractions are separately hydrogenated, and the already hydrogenated monosaccharides, disaccharides, oligosaccharides and polysaccharides are converted to such various saccharides. Are added at a ratio determined for each of the components.

For example, the sweetening composition according to the present invention comprises
Manufactured by mixing fractions containing polysaccharides obtained by enzymatic hydrolysis of inulin hydrolyzate, birch tree or corn chunks, starch hydrolysate, dextrin and / or polyglucose The hydrolyzate and this fraction are then mixed in a defined ratio and the mixture thus obtained is hydrogenated.

[0052] Under these conditions, the produced sweet composition simultaneously contains xylitol, arabitol, sorbitol and mannitol, as well as the hydrogenated polysaccharide which is not digested by amyloglucosidase.

As described above, a method for enzymatic hydrogenation of dextrin has already been proposed in the literature.

EP 0368451 describes a process which essentially involves dissolving pyrrodextrin in water and allowing the resulting solution to act with α-amylase. The purpose of this method is to remove odors and tastes from pyrrodextrin to provide a dextrin containing dietary fiber.

Thus, according to the method described in this patent, the pyrodextrin is decomposed into water and then hydrolyzed with α-amylase. However, α
-After the amylase treatment, other enzymes may be added: this may be transglucosidase, β-amylase, glucoamylase. The product obtained by this enzymatic treatment is then subjected to hydrogenation. Monosaccharides and oligosaccharides can be added to the initial starch to be dextrinized to increase the concentration of undigested dextrin in the final product.

The object of the above patent is therefore to provide a product consisting essentially of a polysaccharide which is very hard to digest and which is "low calorie", acts as a dietary fiber and is essentially very hard to digest. Is to do. Thus, the content of the product exemplified by its "non-digestible dextrin" is between about 27-95% and the concentration of polysaccharides with a degree of polymerization of 4 or more in these products is about 60-92%. % By weight.

Further, another method for obtaining dietary fiber from dextrin is described in Japanese Patent Application JP-A-62091501. This process essentially involves treating the hydrogenated starch hydrolyzate at an elevated temperature by heating under anhydrous conditions at 150-250 ° C. in the presence of a catalyst consisting of an inorganic or organic acid. .

Thus, as in the above-mentioned patent application, this document also relates to the production of a product which is very difficult to digest in the body and is therefore called "low calorie", which acts as a dietary fiber in the body. Therefore, their purpose is
Technical properties consisting of a hydrogenated starch hydrolyzate with sweetness potential, low cariogenicity, can be used in confectionery, chewing gum and toothpaste, and also in elixirs for administration to beverages, drugs or animals The purpose of the present invention is to produce a sweet product having the following.

Furthermore, it can be emphasized that the above references do not describe or suggest the use of an enzyme that hydrolyzes the 1-6 bond of amylopectin. This enzyme is expected to produce a fraction containing a hydrogenated polysaccharide having extremely low digestibility within the scope of the present invention, and has a great advantage.

It is used for preparing a fraction obtained by enzymatic hydrolysis of dextrin and / or polyglucose, of dextrin or of polyglucose, and for producing the low caries-inducing sweet composition according to the invention. The amounts and conditions of action of various enzymes are desirably selected from the following. Amyloglucosidase: 4000-kg dry substrate
500,000 international units, temperature 50-60 ° C, duration of action 30-100 hours, pH 5.0-6.0, β-amylase: 100-10000 per kg dry substrate
LINTNER unit, temperature 50-60 ° C, duration of action 30-100 hours, pH 5.0-6.0, α-amylase: 20-2000 KNU / kg dry substrate
Units (Kilo Nova Units), pH 5.0-6.0, temperature 50-60 ° C, duration of action 16-100 hours, 1-6 bond hydrolase: 150-kg / kg dry substrate
15000 ABM unit (ABM, CHESHIRE, ENGLAND),
Optionally, 50-100 of β-amylase per kg of dry substrate
International units exist, pH 55.0-6.0, temperature 50-60
° C, duration of action 24-100 hours.

The enzymes used are as follows: in the case of amyloglucosidase, fungal amyloglucosidase,
In the case of β-amylase, microorganism or plant β-amylase, α-amylase, bacterial or fungal α-amylase, 1-6 bond hydrolase,
A substance selected from pullulanase and isoamylase; for example, PULLUZYME from ABM or CK20L from AMANO.

Within the scope of the present invention, the hydrolyzate obtained as a result of the enzymatic hydrolysis of dextrin, of polyglucosidase, or of a mixture of dextrin and / or polyglucosidase, comprises additional saccharides, oligosaccharides and polysaccharides. Although it optionally contains sugars and the like,
Hydrogenation of this hydrolyzate is achieved by methods known per se, hydrogenation over RANEY nickel and hydrogenation over precious metals.

The hydrogenation is carried out after purification of the hydrolyzate by working on activated carbon and after desalination on cation and anion resins. The hydrogenation is carried out, for example, over a RANEY nickel catalyst at a temperature of 130 ° C. and a hydrogen pressure of 50 bar.

After hydrogenation, the resulting syrup was filtered,
Dechlorinated to a concentration of commercially available, generally about 7
Concentrate until 0-85 Brix, about 70-85% dry matter is obtained. Then it is dried, for example by spray drying.

Hydrogenation generally involves reducing the remaining reducing sugars to a dry fraction of less than 0.50, preferably less than 0.25,
More preferably, the process is carried out until a ratio of less than 0.20 is reached.

One of the essential characteristics of the sweetening composition of the present invention is that it has low caries induction. That is, the rate of acidification caused by bacteria present in the mouth can be suppressed lower than conventional daily sugars such as glucose, fructose, sucrose or glucose syrup.

According to a preferred embodiment of the present invention, the sweetening composition of the present invention has properties which can be described as being low cariogenic according to the B test.

This B-test means that the applicant's company
It was developed to examine the non-caries-inducing properties of hydrogenated hydrolysates marketed under the trade name LYCASIN 80/55 since 1980. This simple test is performed in vitro,
It is based on measuring the acidification of a fixed amount of hydrolyzed starch hydrolyzate after inoculation of the culture medium with saliva. It also measures the decrease in pH of the culture containing the test product over time after inoculation with saliva provided by several donors and compares it with a standard culture without carbohydrates. It is based on that. This test is not appropriate for absolute determination of non-cariogenic properties of a product, as the results vary with the type of saliva used. However, reliable comparisons between different products can be made.

The detailed method of this test is as follows. A series of tubes containing 10 ml of sugar-free nutrient-containing medium (triptycase with 2% dry matter)
Prepare under the conditions of H7. The tubes are transferred to an autoclave and sterilized at 120 ° C. for 20 minutes.

A first series of five tubes is filled with 1 ml of sterile water as standard.

A second series of five tubes is injected with 1 ml of an 18% (w / v) solution of the test product.

Then, the five tubes of each series are
Inoculate 0.2 ml per tube with the same volume of diluted human saliva collected from 5 donors.

Then, the production of the acid is examined by measuring the pH. The first measurement is performed before culturing and the subsequent measurements are performed at 30 ° C. after 3, 6, 13, 18, and 21 hours, respectively.

In the products determined to be non-cariogenic based on the B test, the pH measured between the standard product after 21 hours and the test product after 21 hours.
The difference between the two is not very obvious; in fact, the difference is
Should not be larger than units.

One of the great advantages of the present invention is that the sweetening composition, which has a considerable amount of hydrogenated oligosaccharides and polysaccharides, but is non-cariogenic,
It can be supplied based on tests.

Another advantage of the present invention is that it provides a sweetening composition that is stable and that is used as a sweetener and as a medicament in products consumed by humans and animals. These products have a liquid, viscous, doughy, jelly-like, or solid-like structure that is completely compatible with other ingredients contained and optionally mixed in these products There is no problem. These other ingredients include preservatives, emulsifiers, flavors, sugars, polyols, artificial sweeteners, acids,
Pharmaceutical or veterinary ingredients, fats, inorganic or organic fillers such as polydextroses, fibers,
Organic or inorganic gelling reagents such as fructooligosaccharides, gums, proteins, pectin, modified cellulose, algae,
Species extracts, bacteria, polysaccharides, silica and the like.

These products are ingested by humans and animals, and can be orally administered in liquid or viscous liquid structures such as drinks, syrups, emulsions, suspensions, elixirs and mouthwashes; candy, jelly, gum, Dough-like structure such as non-crystalline or semi-crystalline confectionery products such as chew paste, caramel, chewing gum, paddy, cereal bar; food gel, custard tart, jam, jelly, milk dessert, pharmaceutical and Jelly-like structures such as veterinary gels, toothpastes; pastries, biscuits, bakery products, tablets, garnishes, sweet and fragrant powders,
Some are solid structures, such as lyophilized pharmaceutical or veterinary products.

Another advantage of the compositions containing hydrogenated saccharides of the present invention is that they are particularly stable against microbial enzymes and against oxidizing and reducing chemicals.

This advantage can also be exploited in the formation and manufacture of products that are not consumed by humans or animals. For example, there are fields such as cosmetic products, plastics, metal cooling, skin handling, and molds.

The following examples are not intended to limit the scope of the present invention, but rather illustrate the present invention more clearly.

[0081]

【Example】

(Example 1) Yellow dextrin TACKIDEX DF 165
Was dissolved in water to a dry matter content of 35%, and 20 liters of a syrup obtained was stirred in a 25 liter tank to a constant temperature.

The pH was adjusted to 5.5 by using concentrated sodium hydroxide and the tank was kept at 55 ° C. until the following was added: β-amylase SPEZYME DBA from GENENCOR was 0.015. %, 0.2% of pullulanase PULLUZYME 750 L from ABM.

After saccharification for 48 hours, 0.1% of α-amylase MAXAMYL HT 3000 from GISTBROCADES was added. Saccharification stopped after 88 hours.

Then, this syrup was added to 35% (v /
v) H2O2 solution at 0.8% (v / v) at 70 ° C, pH
Treatment was performed for 24 hours under the conditions of 9.5. The remaining hydrogen peroxide was decomposed by adding a small amount of catalyst, and then the syrup was deoxygenated under vacuum and desalted on a mixed resin bed before treatment with activated carbon.

The syrup was then concentrated to a dry matter content of 40% and hydrogenated at a temperature of 130 ° C. and a hydrogen pressure of 50 bar by using a 5% RANEY nickel catalyst. Hydrogenation was continued until the reducing sugar reached a level below 0.5%.

(Composition A) This syrup of the present invention is hereinafter referred to as "base syrup", but maltitol 15.3
%, Polysaccharide 2 with DP equal to or greater than 20
2.4% and analyzed by the F test as 16.2% polysaccharide not hydrolyzed by amyloglucosidase, a portion of this syrup, the added maltitol makes up 40% of the dry matter content of the total composition. The composition containing the hydrogenated saccharide of the present invention was obtained in the ratio shown, in addition to the crystallized maltitol.

(Composition B) Another part of this base syrup was that the xylitol added was 6% of the dry matter content of the total composition.
A composition B containing the hydrogenated saccharide of the present invention was obtained in addition to crystallized xylitol at a ratio indicating 0%.

Thereafter, the composition A and the composition B containing the hydrogenated saccharide of the present invention are concentrated until the dry matter content becomes 75%.

These compositions gave the following carbohydrate spectra in addition to the results obtained in the F-test and the A-test as shown in (Table 1).

[0090]

[Table 1]

A test for caries induction according to the B test was carried out on composition A and composition B. The differences in pH between the standard and composition A and between the standard and B were analyzed to be 0.90 and 0.80, respectively. Composition A
And B were not caries-inducing according to the B test.

Example 2 Another base syrup was prepared by performing the method described below.

[0093] Yellow dextrin TACKIDEX DF 165
Was dissolved in water to a dry matter content of 35%, and 20 liters of a syrup obtained was stirred in a 25 liter tank to a constant temperature.

The pH was adjusted to 5.5 and the temperature was adjusted to 55 ° C. Per kg of dextrin, MILES amyloglucosidase OPTIDEX C 300 0.05% and GIST-BROCADE
The α-amylase MAXAMYL HT 3000 from Company S was added, followed by saccharification for 60 hours.

The syrup obtained was treated with hydrogen peroxide as described in Example 1 before treatment with activated carbon and then desalted on a mixed resin bed. And 50 in dry matter
The mixture was concentrated to%. This syrup has 45% pure glucose and 55% oligo and polysaccharides.
Contained.

The syrup was converted to the sodium form by crosslinking with divinylbenzene and fractionated by chromatography on a column containing a strong cationic resin having a particle size of 0.2 to 0.4 mm: This resin includes
Resin C204 marketed by DUOLITE was used. Fractionation was performed by packing 0.15 liters of syrup in a 2 meter high column containing 1.50 liters of resin. Elution was carried out using water at a temperature of 60 ° C. and a particle speed of 0.85 l / h.

The eluate was fractionated into two. One corresponds to the early part of the elution and contains polysaccharides. The other corresponds to the latter part of the elution and contains substantial glucose.

The eluate corresponding to the polysaccharide-rich fraction was concentrated and readjusted to obtain a polysaccharide syrup. The carbohydrate spectrum of the syrup was determined by high performance liquid chromatography and the results are shown in Table 2.

[0099]

[Table 2]

This syrup, hereinafter referred to as polysaccharide syrup, is used as a basis for preparing the compositions C and D of the present invention.

(Composition C) Crystallized xylose was dissolved in a polysaccharide to represent 50% of the dry matter content of the total composition, and the resulting syrup was hydrogenated, purified,
It was further concentrated by a known method.

(Composition D) Crystallized xylose was dissolved in the same polysaccharide so as to represent 66% of the dry matter content, and the resulting syrup was hydrogenated, purified and further purified by the known method. Concentrated by the method.

In this way, a syrup was obtained, and its composition with respect to the dry matter content is shown in Table 3.

[0104]

[Table 3]

Example 3 Using the polysaccharide syrup obtained according to Example 2 and having the composition shown in Table 2,
Mixing with crystallized isomaltulose marketed by the company MITSUI resulted in a mixture which each contained the following: 35% isomaltulose (on dry substrate) 50% isomaltulose (on dry substrate) Isomaltulose 66% (based on dry substrate) and these syrups are hydrogenated and purified to give a carbohydrate spectrum according to the invention and as shown in Table 4 (expressed as% of dry matter content) Were concentrated to obtain compositions E, F and G having

[0106]

[Table 4]

Example 4 A 20 liter syrup obtained by dissolving the yellow dextrin TACKIDEX DF 165 marketed by the applicant's company in water to 35% dry matter is added to a 25 liter tank. Inside, the mixture was stirred and kept at a constant temperature. The pH of the syrup was adjusted to 5.5, the temperature was adjusted to 55 ° C, and the following were added. GENENCOR β-amylase Spezyme DBA
15% (w / dry w) with ABM Pullulanase Pulluz
yme 750 L 0.2%.

After 86 hours, the mixture was acidified to pH 3.5 and the tank was emptied to 80 to control the enzyme.
Heated at ° C for 20 minutes.

The syrup was filtered, desalted on a strong cationic weak anionic resin and adjusted to 40% by dry matter.

The hydrolyzate was hydrogenated and 5% Raney nickel catalyst was added to the syrup. Temperature 130
The hydrogenation was carried out at 50 ° C. and a hydrogen pressure of 50 bar. This was continued until the reducing sugar reached a level of less than 0.5%.

Thereafter, the hydrogenated hydrolyzate was purified and concentrated to a dry matter content of 70%. It contains the following amounts to dry matter: 1% sorbitol, 22% maltitol and isomaltitol, 25% polysaccharide not hydrolyzed according to the F test.

This syrup according to the present invention comprises:
Called hydrogenated syrup S, it is used as a basis for preparing compositions H, I, J according to the invention.

(Composition H) A part of the hydrogenated syrup S was
Diluted to a dry content of 60%.

Manitol, marketed by the applicant's company, was added to this diluted hydrogenated syrup S in such a proportion that mannitol represents 25% of the dry matter of the total composition.
The mixture was stirred until the mannitol was completely dissolved and concentrated to a dry matter content of 70% to give Composition H.

(Composition I) The following were placed in a 25 liter tank, stirred and kept at a constant temperature of 60 ° C .: 4 kg of hydrogenated syrup S, sorbitol syrup NEOSORB 70/70 marketed by the applicant 16 kg.

Thus, after thoroughly mixing, the composition I
was gotten.

(Composition J) The following were placed in a 25 liter tank, stirred and brought to a constant temperature of 65 ° C .: 10 kg of hydrogenated syrup S, POLYSORB 70/12, a polyol syrup marketed by the applicant / 12 10kg.

The compositions exhibited the following carbohydrate spectra (Table 5).

[0119]

[Table 5]

Compositions H and I were non-cariogenic based on the B test. Composition J was determined to be low cariogenic.

Composition H was found to be very useful for producing sugarless candy that was not very hygroscopic.

Composition I gave good results in the manufacture of toothpastes because of its excellent jelly-like structure combined with silica.

Finally, Composition J was used to make a silica-coated mold. It was an excellent binder, a tackifier.

Example 5 Preparation of a non-caries-inducing chew paste containing four compositions according to the present invention. Compositions A, B, obtained according to Examples 1 and 2, for producing non-cariogenic chew pastes
C and D were used.

Crystallized xylitol and syrup LYCASIN 8
A standard chew paste was prepared using a mixture with 0/55. The four formulations have the same xylitol concentration.

The recipe before boiling the chewing paste is shown in Table 6 (expressed in grams).

[0127]

[Table 6]

(1) P%: In the case of a mixture of the polysaccharide precipitated with alcohol and the polyol used, the polysaccharide is not hydrolyzed based on the A test. (2) Polyol%: The amount of polyol present in the mixture of polyols used.

To produce the chewing paste, the mixture of polyols is brought to a defined temperature (130 ° C. or 14 ° C.).
5 ° C.), boil at atmospheric pressure; cool the mixture to 110 ° C., add fat, emulsifier and gelatin solution, stretch the resulting paste and then shape or cut.

Table 7 shows the flow characteristics of the obtained chewing paste.

[0131]

[Table 7]

It has been found that compositions A, B, C, D are capable of producing non-caries-inducing chew pastes containing xylitol, compared to the possibilities provided in the prior art. In addition, the chew paste can have good machinability and appropriate strength during storage.

Example 6 Production of low caries-inducing candy having a composition according to the present invention. Compositions F and G obtained according to Example 3 are used to make candy. These two compositions, having a dry content of 75%, are heated to 140 ° C, 145 ° C,
Dewater by boiling at 0 ° C and 160 ° C.

A standard candy is prepared by boiling ISOMALT (an equimolar mixture of isomaltitol and glucopyranoside-1,6-mannitol) at the same temperature.

After boiling, candy was obtained, and the water content of the candy was found to be as shown in Table 8.

[0136]

[Table 8]

The dehydration of compositions F and G according to the present invention
It was found to be easier than that of ISOMALT syrup. Less energy is required to boil the composition according to the invention. In the case of conventional sweetened candy, a water content of 2 to 3% is required to provide a candy with good stability despite its low boiling point. Furthermore, the obtained candy is only low caries-inducing.

[0138]

As described above, according to the present invention,
It is possible to provide a composition comprising a low caries-inducing hydrogenated saccharide for use as a sweetening composition or as a medicament in a food, pharmaceutical or veterinary product.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07H 3/04 C07H 3/04 3/06 3/06

Claims (14)

(57) [Claims] 1. The concentration is expressed in terms of the weight of the composition based on dry matter, and the concentration of hydrogenated monosaccharide is 0.1 to 80%, preferably 0.1.
-75%, more preferably 0.1-70%, and the concentration of hydrogenated disaccharide is 0.1-96%, preferably 0.2.
９４94%, more preferably 0.3-90%, and the concentration of hydrogenated monosaccharide and disaccharide is 11-96 by weight.
%, Preferably 22 to 94%, more preferably 35 to
90%, the concentration of polysaccharides not hydrolyzed by amyloglucosidase in the F test (described below) is 1 to 40 by weight
%, Preferably 1.5 to 30%, more preferably 3 to 30%.
A composition comprising a low caries-inducing hydrogenated saccharide comprising 26.5% and a 100% balance of hydrogenated oligosaccharides and polysaccharides. 2. The method according to claim 1, wherein the hydrogenated monosaccharide is sorbitol, mannitol, galactitol, xylitol, threitol,
The composition comprising a low caries-inducing hydrogenated saccharide according to claim 1, which is selected from the group comprising arabitol and erythritol. 3. The hydrogenated disaccharide is selected from the group including maltitol, hydrogenated maltulose, hydrogenated isomaltulose, isomaltitol, lactitol and hydrogenated inurobiose. 3. A composition comprising the low caries-inducing hydrogenated saccharide according to 1 or 2. 4. The hydrogenated oligosaccharides and polysaccharides are maltotriitol, maltotetriitol, inulotriitol, hydrogenated oligosaccharides and polysaccharides obtained by hydrolysis of starch following hydrogenation, cellobiitol. Characterized by being selected from the group comprising hydrogenated oligosaccharides and polysaccharides obtained by the hydrolysis of cellotriitol, xylobiitol, xylotriitol, and cellulose subsequent to hydrogenation, xylans or fractionation. A composition comprising the low caries-inducing hydrogenated saccharide according to any one of claims 1 to 3. 5. The concentration is expressed by weight relative to the dry matter of the composition, the concentration of hydrogenated monosaccharide being 0.1 to 65%, preferably 0.1.
And the weight concentration of the hydrogenated disaccharide is 10 to 96%, preferably 1 to 60%.
5 to 94%, more preferably 15 to 90%, wherein the weight concentration of the ethanol-precipitated polysaccharide and the polysaccharide not hydrolyzed by amyloglucosidase in the A test is 1 to 30%, preferably 1.5 to 25%. %, More preferably 2 to 15%, wherein the composition comprises a low caries-inducing hydrogenated saccharide, characterized in that the hydrogenated oligosaccharide or polysaccharide has a 100% balance. 6. The composition comprising a low cariogenic hydrogenated saccharide according to claim 1, which is not cariogenic based on the B test. 7. A polysaccharide not hydrolyzed by amyloglucosidase is obtained by enzymatic treatment of dextrin and / or polyglucose, and this enzymatic treatment has at least a saccharifying enzyme activity such as amyloglucosidase or β-amylase. The composition comprising a low caries-inducing hydrogenated saccharide according to any one of claims 1 to 6, wherein the obtained hydrolyzate is subsequently hydrogenated. 8. The conditions for the enzymatic treatment of dextrin and / or polyglucose are selected such that the hydrolyzate obtained at the end of this treatment has a DE of 5 to 80, preferably 10 to 65. A composition comprising the low caries-inducing hydrogenated saccharide according to claim 7. 9. First, by subjecting dextrin or polyglucose to an enzymatic treatment including at least a saccharifying enzyme such as amyloglucosidase or β-amylase, a fraction containing a polysaccharide not hydrolyzed by amyloglucosidase is obtained. The treatment conditions were selected such that the hydrolyzate obtained at the end of the treatment had a DE of 5 to 80, preferably 10 to 65. Then, the monosaccharide, disaccharide and disaccharide were added to the fraction. 9. The method according to claim 1, wherein oligosaccharides and polysaccharides are added in accordance with the determined ratio of each component, and the composition thus obtained is hydrogenated. A method for producing a composition containing a hydrogenated saccharide. 10. First of all, by subjecting at least one of dextrin and / or polyglucose to an enzymatic treatment having a saccharifying enzyme such as amyloglucosidase or β-amylase, the amount of dextrin and / or polyglucose not digested by amyloglucosidase is increased. A fraction containing a saccharide is prepared, and the treatment conditions at this time are such that the hydrolyzate obtained at the end of the treatment has a DE of 5 to 80, preferably 10 to
65, then hydrogenate this fraction and add to this hydrogenated fraction hydrogenated monosaccharides, disaccharides, oligosaccharides and polysaccharides according to the determined proportions of each component A method for producing a composition containing a low caries-inducing hydrogenated saccharide according to any one of claims 1 to 8. 11. An enzymatic treatment having at least a saccharifying enzyme activity is carried out simultaneously with the treatment with α-amylase.
Alternatively, it is performed later.
5. A method for producing a composition comprising a low caries-inducing hydrogenated saccharide according to the above. 12. The method according to claim 9, wherein the enzyme treatment having at least a saccharifying enzyme action is performed before, simultaneously with, or after the treatment with an enzyme that hydrolyzes the 1-6 bond of amylopectin. A method for producing a composition comprising a low caries-inducing hydrogenated saccharide according to any one of the above. 13. The amounts and working conditions of the various enzymes used during the enzymatic treatment are determined by comparing amyloglucosidase: 400 kg / dry substrate.
0 to 500,000 international units, temperature 50 to 60 ° C., action time 30 to 100 hours, pH 5.0 to 6.0, β-amylase: 100 to 1 per kg of dry substrate
0000 LINTNER unit, temperature 50-60 ° C, action time 30-100 hours, pH 5.0-6.0, α-amylase: 20-20 for 1 kg of dry substrate
00 KNU units (Kilo Nova Units), pH 5.0
6.0, temperature 50-60 ° C, action time 16-100 hours, enzyme that hydrolyzes 1-6 bond of amylopectin: 150-15000 ABM unit / kg dry substrate, 50-100 international per kg dry substrate Units of β-amylase are optionally present, pH 5.0-6.0, temperature 50-
The method for producing a composition containing a low caries-inducing hydrogenated saccharide according to any one of claims 9 to 12, wherein the composition is selected from the group consisting of 60 ° C and 24 to 100 hours. 14. The low caries-inducing hydrogenated saccharide according to claim 1, wherein the hydrogenated saccharide is used as a sweet composition or as a drug contained in a product consumed by humans or animals. use of a composition comprising a.